WO2017082546A1 - Bouillie d'anode pour batterie secondaire permettant d'améliorer la dispersibilité et de réduire la résistance et anode la comprenant - Google Patents

Bouillie d'anode pour batterie secondaire permettant d'améliorer la dispersibilité et de réduire la résistance et anode la comprenant Download PDF

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WO2017082546A1
WO2017082546A1 PCT/KR2016/011767 KR2016011767W WO2017082546A1 WO 2017082546 A1 WO2017082546 A1 WO 2017082546A1 KR 2016011767 W KR2016011767 W KR 2016011767W WO 2017082546 A1 WO2017082546 A1 WO 2017082546A1
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negative electrode
cmc
slurry
secondary battery
active material
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PCT/KR2016/011767
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English (en)
Korean (ko)
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유정우
조형석
노예철
우경화
정광호
김제영
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주식회사 엘지화학
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Priority to JP2017559667A priority Critical patent/JP6659012B2/ja
Priority to US15/569,633 priority patent/US10644316B2/en
Priority to EP16864472.2A priority patent/EP3276714B1/fr
Priority to PL16864472T priority patent/PL3276714T3/pl
Priority to CN201680027429.7A priority patent/CN107534153B/zh
Publication of WO2017082546A1 publication Critical patent/WO2017082546A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Definitions

  • the present invention relates to a negative electrode slurry for secondary batteries, which improves dispersibility and reduces battery resistance by controlling physical properties such as substitution degree and molecular weight of CMC.
  • the lithium secondary battery includes a positive electrode including a positive electrode active material capable of inserting / desorbing lithium ions, a negative electrode containing a negative electrode active material capable of inserting / removing lithium ions, and an electrode having a microporous separator interposed between the positive electrode and the negative electrode. It refers to a battery containing a nonaqueous electrolyte containing lithium ions in the assembly.
  • the most important task in the preparation of the negative electrode slurry for the production of the negative electrode is to increase the dispersibility of the negative electrode active material.
  • a thickener which serves as a dispersant, is added in order to have sufficient dispersibility. If the thickener is added in an excessively small amount, dispersion of the negative electrode active material in the negative electrode slurry becomes insufficient, resulting in formation of large aggregates or settling of the slurry. In coating the current collector, problems such as filter clogging and electrode surface defects may occur. On the other hand, if the thickener is excessively added, it may cause a problem that the resistance of the negative electrode increases by preventing the movement of lithium ions in the negative electrode. Therefore, minimizing the amount of thickener to reduce the resistance of the negative electrode while maintaining sufficient dispersibility has become the most important task.
  • the present inventors have studied carboxy methyl cellulose (CMC) as a thickener, and found that the adsorption amount of CMC adsorbed on the negative electrode active material varies depending on the properties of the degree of substitution or molecular weight of CMC. And the viscosity and sedimentation change was compared while changing the compounding amount, and finally it was possible to manufacture a secondary battery with reduced resistance while producing a negative electrode slurry excellent in dispersibility while reducing the compounding amount of CMC.
  • CMC carboxy methyl cellulose
  • the problem to be solved of the present invention is to improve the dispersibility of the negative electrode active material by increasing the adsorption amount of the CMC to the negative electrode active material by controlling the physical properties such as the degree of substitution and molecular weight of the CMC, while at the same time reducing the amount of CMC slurry solids It is to provide a negative electrode slurry for a secondary battery and a negative electrode comprising the same, which increases and decreases the resistance of the battery.
  • the present invention is to solve the above problems, a negative electrode slurry containing a negative electrode active material and a thickener, the negative electrode active material has a tap density of 1.0 g / cc or less, the slurry solids content relative to the total weight of the slurry Provided is a negative electrode slurry for secondary batteries of 48 wt% or more.
  • the present invention also provides a secondary battery negative electrode including the secondary battery negative electrode slurry, and a lithium secondary battery including the secondary battery negative electrode, a battery module and a battery pack including the same.
  • the negative electrode slurry for secondary batteries of the present invention has the effect of increasing the solids content and reducing the resistance of the battery by improving the dispersibility of the negative electrode active material by increasing the adsorption amount of CMC to the negative electrode active material, and at the same time reducing the compounding amount of the CMC. have.
  • the present invention provides a negative electrode slurry comprising a negative electrode active material and a thickener, the negative electrode active material has a tap density of 1.0 g / cc or less, the slurry solids content of more than 48 wt% of the total weight of the slurry provides a negative electrode slurry for secondary batteries do.
  • Thickener is a cellulose-based polymer, carboxy methyl cellulose (CMC), methyl cellulose (methyl cellulose, MC), hydroxypropyl cellulose (HPC), methyl hydroxypropyl
  • CMC carboxy methyl cellulose
  • MC methyl cellulose
  • HPC hydroxypropyl cellulose
  • cellulose methyl hydroxypropyl cellulose
  • EHEC ethyl hydroxyethyl cellulose
  • MEHEC methyl ethyl hydroxyethyl cellulose
  • It may be more than, specifically, may be carboxy methyl cellulose (CMC).
  • the carboxymethyl cellulose has a property that can provide additional thickening and excellent coating properties and at the same time contribute to the adhesion with the current collector to prevent the active material from falling off from the current collector and exhibit an excellent cycle characteristics.
  • the negative electrode active material according to the embodiment of the present invention may have a tap density of 1.0 g / cc or less.
  • the tap density is a mass per volume of the powder composed of particles, and refers to a density that fills a gap between particles by constant tapping or vibration. Factors affecting the tap density include particle size distribution, moisture content, particle shape, cohesiveness, and the like.
  • the tap density can predict the fluidity and the compressibility of the material.
  • the slurry solids is a weight ratio of the solid component in the slurry to the total weight of the slurry, and is calculated as (weight of the solid component) / (weight of the solid component + weight of the liquid component) according to each compounding amount actually used, and the final slurry is After drying, remove all the water and measure the remaining weight.
  • the solid component may mean an actual amount of the active material, the conductive material, the CMC thickener and the SBR binder, and the liquid component may mean water contained in the CMC and SBR solution and water which may be additionally added for viscosity control.
  • achieving a slurry solid content of 48 wt% is more than that of a negative electrode active material having a tap density of 1.0 g / cc or more. It is a difficult task.
  • the present invention solves the above problems, by controlling the adsorption amount of the CMC to the negative electrode active material by adjusting the physical properties such as the degree of substitution or molecular weight of the CMC, it can exhibit excellent dispersibility of the negative electrode active material and reduce the resistance of the battery
  • a CMC By including a CMC, it was possible to achieve a slurry solids content of 48 wt% or more while using a negative electrode active material having a tap density of 1.0 g / cc or less.
  • the carboxymethyl cellulose (CMC) may have an adsorption amount (hereinafter, CMC adsorption amount) to the negative electrode active material is 0.8 wt% or more, particularly preferably 0.8 to 0.9 wt%.
  • the CMC adsorption amount can be measured by the following method.
  • the active material-CMC slurry is prepared by mixing CMC in a ratio of 1.5 wt% or more with respect to the defined active material. After diluting this slurry five times in distilled water, the CMC that is not adsorbed to the distilled water and the active material is filtered through filtration using a vacuum flask. The residual slurry after filtration was dried using a TGA (thermogravimetric analyzer) in a nitrogen atmosphere and then heated up to 500 ° C. or higher at room temperature to check the weight loss.
  • TGA thermogravimetric analyzer
  • the CMC weight ratio (adsorbed CMC weight / active material-CMC total weight) adsorbed relative to the active material can be measured through this.
  • the adsorption amount is less than 0.8 wt%, the dispersion becomes insufficient, so that the negative electrode active material particles form aggregates, and thus, the coating may not be performed smoothly, and the performance as an electrode may be degraded.
  • Increasing the compounding amount it is difficult to achieve the purpose of producing a negative electrode slurry of more than 48 wt% solids concentration, another problem that is difficult to dry after coating as the slurry solids are reduced, which makes it difficult to form a uniform electrode, thereby reducing the performance of the battery Can occur.
  • the amount of adsorption is greater than 0.9 wt%, an excess of CMC may be adsorbed on the surface of the negative electrode active material, thereby preventing the movement of lithium ions, thereby causing a problem of increasing resistance inside the battery.
  • the negative electrode slurry for a secondary battery according to an embodiment of the present invention includes a CMC having an adsorption amount for the negative electrode active material in the above range, so that a sufficient amount of hydrophilic CMC is adsorbed onto the surface of the hydrophobic negative electrode active material, so that each negative electrode active material The particles are less likely to form aggregates, whereby the dispersed state is good. Therefore, the slurry solids content of 48 wt% or more can be achieved through a low CMC compounding amount, and at the same time, a cathode having excellent dispersibility and low resistance can be manufactured.
  • the amount of CMC adsorption can be achieved through the control of physical properties such as substitution degree and molecular weight of CMC.
  • the carboxymethyl cellulose (CMC) may use a CMC having a degree of substitution (DS) of 0.7 to 1.3, more preferably 0.7 to 0.9.
  • DS degree of substitution
  • Degree of substitution also referred to as degree of etherification, refers to the number (average value) of hydroxyl groups substituted with carboxymethyl groups among the three hydroxyl groups (OH groups) in the glucose cyclic constituting cellulose, and the value is theoretically between 0 and 3. In general, the higher the degree of substitution, the more hydrophilic it becomes and the easier it is to dissolve.
  • the degree of substitution is less than 0.7, the water solubility is low, so that when dissolved in distilled water is not completely dissolved, many undissolved so-called microgels are left, which is a major cause of additional surface aggregation and poor electrode surface after coating during slurry production. If the degree of substitution is more than 0.9, the hydrophilicity is increased, solubility is improved, but the affinity with the active material is lowered may cause a problem that the adsorption amount is reduced.
  • Carboxymethyl cellulose (CMC) may use a CMC having a molecular weight of 700,000 to 4.2 million, more preferably 700,000 to 3.5 million.
  • the molecular weight of CMC refers to a weight average molecular weight (Mw), and refers to a value measured by Gel Permiation Chromatography (GPC) -Refractive Index (RI).
  • the negative electrode active material When the molecular weight is less than 700,000, the negative electrode active material may not be evenly dispersed due to the decrease of the attractive force between the polymers forming the network when the network is formed by the thickener, and the adhesive force of the active material may be lowered, which may adversely affect the life span.
  • the viscosity if the viscosity is greater than 3.5 million, the viscosity of the slurry may be so high that the coating is difficult because the viscosity at the same concentration is too high, and to prevent this, if the viscosity is reduced by further distilled water, the solid content of the slurry is reduced. Another problem may arise where the productivity of the electrode is degraded.
  • the present invention includes a low molecular weight CMC having a molecular weight of 1 million or less and a high molecular weight CMC having a molecular weight of 2 million or more, wherein the blending ratio of the low molecular weight CMC: high molecular weight CMC is 1: 3 to 3: 1 by weight.
  • the compounding ratio it was possible to use the CMC satisfying the weight average molecular weight range of the present invention.
  • Carboxymethyl cellulose (CMC) may be included in less than 1 wt% of the total weight of the negative electrode slurry.
  • the amount of the CMC is reduced too much, the dispersion of the negative electrode active material becomes insufficient, and the particles of the negative electrode active material form large aggregates. In this case, a problem may occur that the filter is clogged by the aggregates when applied to the current collector. In addition, since a sufficient amount of electrolyte does not reach inside the large aggregates, it may be difficult to move lithium ions, resulting in a problem that the battery capacity becomes small.
  • the present invention provides a negative electrode slurry for secondary batteries having excellent dispersibility while controlling the amount of CMC blended according to the amount of CMC adsorbed on the negative electrode active material, thereby minimizing the amount of CMC blended to reduce internal resistance of the battery. Therefore, the negative electrode slurry of the secondary battery of the present invention may include CMC in an amount of 1 wt% or less based on the total weight of the negative electrode slurry.
  • a negative electrode slurry for a secondary battery according to an embodiment of the present invention is characterized in that the slurry sedimentation rate is 7% or less.
  • the slurry sedimentation rate is calculated by dividing the height of the sinking portion of the slurry by the initial height four days after the slurry production.
  • the amount of CMC compounding can be reduced to increase the slurry solids content to 48 wt% or more, and a negative electrode slurry having excellent dispersion stability with a slurry settling rate of 7% or less is produced. You can do it.
  • the reduction of the CMC compounding amount makes it possible to fabricate a negative electrode having a low resistance of the battery.
  • the lower limit of a slurry sedimentation rate is not specifically limited.
  • the binder according to an embodiment of the present invention is a copolymer of styrene-butadiene rubber (SBR), polyvinylidene fluoride (PVdF), polyhexafluoropropylene-polyvinylidene fluoride (PVdF / HFP ), Poly (vinylacetate), polyvinyl alcohol, polyethylene oxide, polyvinylpyrrolidone, alkylated polyethylene oxide, polyvinyl ether, poly (methyl methacrylate), poly (ethyl acrylate), polytetrafluoroethylene ( PTFE), polyvinylchloride, polyacrylonitrile, polyvinylpyridine, acrylonitrile-butadiene rubber and ethylene propylene diene monomer (EPDM), and more preferably styrene-butadiene rubber ( Styrene-Butadiene Rubber, SBR).
  • SBR styrene-butadiene Rubber
  • SBR St
  • the styrene-butadiene rubber has a strong adhesive force and can produce a binder effect even in a small amount.
  • the styrene-butadiene rubber has a high water solubility and has good properties as a thickener and a styrene-butadiene rubber as a binder to prepare an aqueous electrode. Suitable.
  • the solvent used for preparing the negative electrode slurry for secondary batteries according to an embodiment of the present invention may be used without particular limitation as long as it dissolves CMC appropriately.
  • the solvent may be uniformly mixed with water or water as an aqueous solvent.
  • An organic solvent lower alcohol, lower ketone, etc.
  • NMP N-methyl pyrrolidone
  • the present invention is a lithium secondary battery comprising a secondary battery negative electrode and a positive electrode, a negative electrode, an electrolyte and a separator comprising the negative electrode slurry for the secondary battery, wherein the negative electrode comprises a negative electrode slurry for a secondary battery of the present invention To provide.
  • the lithium secondary battery of the present invention can be prepared according to conventional methods known in the art. For example, it can be prepared by inserting a separator between the positive electrode and the negative electrode and the electrolyte solution in which lithium salt is dissolved.
  • the electrode of the secondary battery may also be manufactured by a conventional method known in the art, for example, a slurry is prepared by mixing and stirring a solvent, a binder, a conductive material, and a thickener in a positive electrode active material or a negative electrode active material, if necessary, and then stirring the same.
  • the electrode may be prepared by coating (coating) the metal current collector, compressing it, and drying the same.
  • a lithium transition metal oxide may be preferably used.
  • Li x CoO 2 (0.5 ⁇ x ⁇ 1.3), Li x NiO 2 (0.5 ⁇ x ⁇ 1.3), Li x MnO 2 (0.5 ⁇ x ⁇ 1.3), Li x Mn 2 O 4 (0.5 ⁇ x ⁇ 1.3), Li x (Ni a Co b Mn c ) O 2 (0.5 ⁇ x ⁇ 1.3, 0 ⁇ a ⁇ 1, 0 ⁇ b ⁇ 1, 0 ⁇ c ⁇ 1, a + b + c 1), Li x Ni 1-y Co y O 2 (0.5 ⁇ x ⁇ 1.3, 0 ⁇ y ⁇ 1), LixCo 1-y Mn y O 2 (0.5 ⁇ x ⁇ 1.3, 0 ⁇ y ⁇ 1), Li x Ni 1-y Mn y O 2 (0.5 ⁇ x ⁇ 1.3, O ⁇ y ⁇ 1), Li x (Ni a Co b M
  • a carbon material lithium metal, silicon, tin, or the like, in which lithium ions may be stored and released, may be used.
  • a carbon material may be used, and as the carbon material, both low crystalline carbon and high crystalline carbon may be used.
  • Soft crystalline carbon and hard carbon are typical low crystalline carbon, and high crystalline carbon is natural graphite, Kish graphite, pyrolytic carbon, liquid crystal pitch carbon fiber.
  • High temperature calcined carbon such as mesophase pitch based carbon fiber, mesocarbon microbeads, mesophase pitches and petroleum or coal tar pitch derived cokes.
  • the current collector of the metal material is a metal having high conductivity and which the slurry of the electrode active material can easily adhere to, and can be used as long as it is not reactive in the voltage range of the battery.
  • Non-limiting examples of the positive electrode current collector is a foil produced by aluminum, nickel or a combination thereof
  • non-limiting examples of the negative electrode current collector is produced by copper, gold, nickel or copper alloy or a combination thereof Foil and the like.
  • the conductive material is not particularly limited as long as it can be generally used in the art, for example, artificial graphite, natural graphite, carbon black, acetylene black, ketjen black, denka black, thermal black, channel black, carbon fiber, metal fiber , Aluminum, tin, bismuth, silicon, antimony, nickel, copper, titanium, vanadium, chromium, manganese, iron, cobalt, zinc, molybdenum, tungsten, silver, gold, lanthanum, ruthenium, platinum, iridium, titanium oxide, polyaniline, Polythiophene, polyacetylene, polypyrrole or a combination thereof may be applied, and in general, a carbon black conductive material may be frequently used.
  • Thickener and binder according to an embodiment of the present invention is as described above will be omitted.
  • the electrolyte solution included in the lithium secondary battery according to the present invention is propylene carbonate (PC), ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl carbonate (DPC), dimethyl sulfoxide, acetonitrile , Dimethoxyethane, diethoxyethane, tetrahydrofuran, N-methyl-2-pyrrolidone (NMP), ethylmethyl carbonate (EMC), gamma butyrolactone (GBL), fluoroethylene carbonate (FEC), methyl formate And at least one mixed organic solvent selected from the group consisting of ethyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate, pentyl acetate, methyl propionate, ethyl propionate, ethyl propionate and butyl propionate.
  • PC propylene carbonate
  • the electrolyte according to the present invention may further comprise a lithium salt, the lithium salt of the anion is F -, Cl -, Br - , I -, NO 3 -, N (CN) 2 -, BF 4 -, ClO 4 -, PF 6 -, (CF 3) 2 PF 4 -, (CF 3) 3 PF 3 -, (CF 3) 4 PF 2 -, (CF 3) 5 PF -, (CF 3) 6 P - , F 3 SO 3 -, CF 3 CF 2 SO 3 -, (CF 3 SO 2) 2 N -, (FSO 2) 2 N -, CF 3 CF 2 (CF 3) 2 CO -, (CF 3 SO 2 ) 2 CH -, (SF 5 ) 3 C -, (CF 3 SO 2) 3 C -, CF 3 (CF 2) 7 SO 3 -, CF 3 CO 2 -, CH 3 CO 2 -, SCN - and ( CF 3 CF 2 SO 2
  • the lithium secondary battery according to the present invention may be a cylindrical, square, or pouch type secondary battery, but is not limited thereto.
  • the present invention provides a battery module including the lithium secondary battery as a unit cell and a battery pack including the same.
  • the battery pack includes a power tool; Electric vehicles including electric vehicles (EVs), hybrid electric vehicles (HEVs), and plug-in hybrid electric vehicles (PHEVs); Or it can be used as one or more medium-large device power source selected from the group consisting of a power storage system.
  • Electric vehicles including electric vehicles (EVs), hybrid electric vehicles (HEVs), and plug-in hybrid electric vehicles (PHEVs); Or it can be used as one or more medium-large device power source selected from the group consisting of a power storage system.
  • a negative active material-CMC slurry was prepared by mixing the following CMC in a proportion of 1.5 wt% or more with respect to the negative electrode active material (artificial graphite having a tap density of 0.74 g / cc). After diluting the slurry by 5 times in distilled water, the CMC that was not adsorbed to the active material was filtered, and then TGA (thermogravimetric analyzer) was used to determine the weight ratio of the adsorbed CMC to the active material (adsorbed CMC weight / total active material-CMC). It was measured, and the results are as shown in Table 1 below.
  • the negative active material artificial graphite having a tap density of 0.74 g / cc
  • the conductive material acetylene black
  • the thickener CMC
  • the binder SBR
  • the negative electrode slurry was applied to a thin copper (Cu) thin film, which is a negative electrode current collector having a thickness of 10 ⁇ m, dried to prepare a negative electrode, and then subjected to roll press to process a negative electrode.
  • Cu copper
  • the positive electrode active material LiNi 0.6 Mn 0.2 Co 0.2 O 2
  • the binder KF1100
  • the conductive material Super-C
  • NMP N-methyl-2-pyrrolidone
  • the positive electrode slurry was applied to one surface of an aluminum (Al) thin film, which is a positive electrode current collector having a thickness of 20 ⁇ m, and dried to prepare a positive electrode, followed by roll pressing to process a positive electrode.
  • Al aluminum
  • Electrolyte solution is a solvent in which ethylene carbonate (Dithyl carbonate), diethyl carbonate (Diethyl carbonate) and dimethyl carbonate (Dimethyl carbonate) are mixed in a volume ratio of 1: 1: 2 to a solvent in which vinylene carbonate is added. It was prepared by dissolving mol of LiPF 6 .
  • the prepared electrolyte solution was injected to complete the production of a lithium secondary battery.
  • a lithium secondary battery was manufactured in the same manner as in Example 1, except that 0.8 wt% of the CMC of Preparation Example 2 was mixed to prepare a negative electrode slurry.
  • a lithium secondary battery was manufactured in the same manner as in Example 1, except that the negative electrode slurry was prepared by mixing 0.9 wt% of the CMC of Preparation Example 3.
  • a lithium secondary battery was manufactured in the same manner as in Example 1, except that 1.8 wt% of the CMC of Preparation Example 4 was mixed to prepare a negative electrode slurry.
  • a lithium secondary battery was manufactured in the same manner as in Example 1, except that 1.4 wt% of CMC of Preparation Example 4 was mixed to prepare a negative electrode slurry.
  • a lithium secondary battery was manufactured in the same manner as in Example 1, except that 0.8 wt% of the CMC of Preparation Example 5 was mixed to prepare a negative electrode slurry.
  • a lithium secondary battery was manufactured in the same manner as in Example 1, except that 1.2 wt% of CMC of Preparation Example 6 was mixed to prepare a negative electrode slurry.
  • the slurry is sufficiently contained in a beaker of 6 cm in diameter and over 5 cm in height, using Brookfiled's viscometer (DV2T (LV), using a spindle with a maximum measurable viscosity of about 10000 cp (63 spindles in this experiment)). The viscosity value measured when rotating at 12 rpm was taken.
  • the slurry sedimentation rate of the negative electrode slurry for secondary batteries according to Examples 1 to 3 and Comparative Examples 1 to 4 was measured, and the results are as shown in Table 2 below. Slurry sedimentation rate was calculated by dividing the height of the solid portion of the slurry by the initial height 4 days after the slurry production.
  • the solid content, viscosity, sedimentation rate, and cell resistance of the slurry vary depending on the degree of substitution, molecular weight, CMC adsorption amount, and slurry blending amount of the CMC.
  • the slurry solids concentration is larger than 48 wt% or more, and the cell resistance is small as compared with Comparative Examples 1 to 4.
  • the CMC compounding amount should be blended at 1.0 wt% or more, 1.8 wt% and 1.4 wt%, respectively, in order to secure stable sedimentation rate. It can be seen that the excess CMC blend reduces slurry solids to 48 wt% or less, 42.9 wt% and 47.8 wt%, respectively. In order to increase the reduced slurry solids to 48 wt% or more, the amount of CMC must be reduced. In this case, there is another problem in that the dispersibility is reduced and the sedimentation rate is increased.
  • Comparative Example 4 when the CMC molecular weight is similar to the Example but the CMC adsorption amount is low as 0.72 wt%, the CMC compounding amount is 1.0 wt% or more, 1.2 wt% It can be seen that it should be increased to, and the excess CMC compounding amount can be seen to reduce the slurry solids to 48 wt% or less, 44.9 wt%.

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
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Abstract

La présente invention concerne une bouillie d'anode pour une batterie secondaire et une anode la comprenant, la dispersibilité d'une matière active d'anode étant améliorée par augmentation de la quantité d'adsorption de CMC par rapport à la matière active d'anode par ajustement du degré de substitution ou des propriétés physiques telles que le poids moléculaire, et la quantité de mélange de CMC étant réduite de manière à accroître la teneur en matières solides de bouillie et à réduire la résistance d'une batterie.
PCT/KR2016/011767 2015-11-11 2016-10-19 Bouillie d'anode pour batterie secondaire permettant d'améliorer la dispersibilité et de réduire la résistance et anode la comprenant WO2017082546A1 (fr)

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JP2017559667A JP6659012B2 (ja) 2015-11-11 2016-10-19 分散性向上及び抵抗減少のための二次電池用負極スラリー、これを含む負極、リチウム二次電池、電池モジュール及び電池パック
US15/569,633 US10644316B2 (en) 2015-11-11 2016-10-19 Anode slurry for secondary battery for improving dispersibility and reducing resistance, and anode comprising same
EP16864472.2A EP3276714B1 (fr) 2015-11-11 2016-10-19 Bouillie d'anode pour batterie secondaire permettant d'améliorer la dispersibilité et de réduire la résistance et anode la comprenant
PL16864472T PL3276714T3 (pl) 2015-11-11 2016-10-19 Zawiesina anodowa dla akumulatora dla poprawy dyspergowalności i zmniejszenia rezystancji oraz zawierająca ją anoda
CN201680027429.7A CN107534153B (zh) 2015-11-11 2016-10-19 用于改善分散性和降低电阻的二次电池用负极浆料、和包含它的负极

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KR101938236B1 (ko) 2019-01-14
EP3276714B1 (fr) 2021-04-28
US20180358622A1 (en) 2018-12-13
EP3276714A1 (fr) 2018-01-31
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US10644316B2 (en) 2020-05-05
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